Highly dispersible anti-microbial and adhesion agents

ABSTRACT

Compositions of matter having anti-microbial properties and/or adhesion properties. The compositions of matter are be highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of the compositions creates a solubility or disperseability for these molecules in aqueous solutions that is not otherwise obtainable.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit to U.S. Non-provisional patent application Ser. No. 15/872,516, filed on Jan. 16, 2018, published as U.S. 2018/0134733 A1 and claiming benefit to U.S. Non-provisional patent application Ser. No. 15/082,026, filed on Mar. 28, 2016, now U.S. Pat. No. 9,902,744 B2, which are incorporated herein by reference in their entirety.

FIELD OF THE DISCLOSURE

The present disclosure relates to compositions of matter having anti-microbial and/or adhesion properties.

BACKGROUND OF THE DISCLOSURE

This invention deals with compositions of matter that have anti-microbial properties and/or adhesion properties and are highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of this invention creates a solubility or disperseability of these molecules in aqueous solutions that is not obtainable from prior art anti-microbial monomers. The inventor herein is not aware of any like molecules in the prior art.

SUMMARY OF THE DISCLOSURE

What is disclosed and claimed herein is a composition of matter having the average general formula:

wherein the average molar ratio of x:y:z is 0.25-3:4:0.25-3, with the proviso that there is present at least one RSi-unit and at least one R′Si unit and W is independently selected from the group consisting essentially of Si, Ti, and Zr, and A1, wherein R is a cure functionality based on the chemistry selected from the group consisting of glycidoxy, amino, acrylamide, methacrylamide, acrylate, methacrylate, C₂-C₈ alkenyl, mercapto, ester, isocyanato, epoxycyclohexyl, carboxylic acid, and O

wherein p has a value of from 1 to 6 and R³ is selected from the group consisting of hydroxyl and alkoxy groups having 1 to 4 carbon atoms.

wherein R² is independently selected from the group consisting of hydroxyl groups,

wherein s has a value of about 1 to 5 and y has a value of 4 wherein R¹ is selected from the group consisting of:

i. a sulfonium salt of the formula:

Si(R⁵)₂C_(d)H_(2d)S⁺(R⁴)₂X⁻,

wherein R⁴ is independently an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, and R⁵ is independently selected from the group consisting of hydroxyl groups,

wherein d is an integer of 1 or greater, and X⁻ is a water soluble monovalent anion;

ii. an isothiuronium salt of the formula:

Si(R⁵)_(2d)C_(d)H_(2d)S⁺C(NH₂)₂X⁻,

wherein R⁵ is independently selected from the group consisting of hydroxyl groups,

wherein d is an integer of 1 or greater, and X⁻ is a water soluble monovalent anion;

iii. a phosphonium salt of the formula:

Si(R⁵)₂C_(d)H_(2d)P⁺(R⁶)₃X⁻,

wherein R⁶ is independently selected from an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, R⁵ is independently selected from the group consisting of hydroxyl groups,

wherein d is an integer of 1 or greater, and X⁻ is a water soluble monovalent anion, and

iv. an amine of the formula:

Si(R⁵)₂C_(d)H_(2d)N(H)(C_(d)H_(2d))NH₂

wherein R⁵ is independently selected from the group consisting of hydroxyl groups,

wherein d is an integer of 1 or greater, and wherein (WO_(y)) is derived from W(OR⁷)₄ wherein (OR⁷) is independently selected from the group consisting of:

-   -   a.—OCH₃,     -   b.—OCH₂CH₃,     -   c.—OCH(CH₃)₂,     -   d.—O(CH₂)₃CH₃,     -   e.—OCH₂CH(CH₃)₂,     -   f.—O(2-ethylhexyl),     -   g. acetoxy, and,     -   h. oximo.

DETAILED DESCRIPTION

It is to be understood that the invention may assume various alternative orientations and step sequences, except where expressly specified to the contrary. It is also understood that the specific devices and processes illustrated in the attached drawings, and described in the specification are simply exemplary embodiments of the inventive concepts disclosed and defined herein. Hence, specific dimensions, directions, steps, or other physical characteristics relating to the various embodiments disclosed are not to be considered as limiting, unless expressly stated otherwise.

The present disclosure relates to compositions of matter and methods of making the same. It is within the scope of this disclosure and as a non-limiting example, the compositions of matter described herein may have anti-microbial and/or adhesion properties. As a result, it is within the scope of this disclosure and as a non-limiting example that the compositions of matter described herein may be useful in killing and/or reducing the number of bacteria, viruses, algae, mildew, and/or mold that may exist on an item.

One method for providing the materials of this invention comprises providing the components:

wherein the molar ratio of x:y:z is 0.25-3:4:0.25-3, p and q are each independently have a value of 2 or less, and co-hydrolyzing the components in the presence of a stoichiometric amount of water, and a catalyst for hydrolysis and condensation.

By careful, controlled hydrolysis of the precursor monomers, one can obtain these materials at very low molecular weights providing a large number of silanols on the molecules, the detail of which can be found infra in the specification, and in the examples.

The materials have the average general formula:

which is derived by the hydrolysis of the silane precursors

in conjunction with the orthosilicate, or orthotitanate, orthozirconate, or orthoaluminate, having the general formula

{W(OR″′)₄}_(y),

wherein the molar ratio of x:y:z is 0.25-3:4:0.25-3.

This hydrolysis is carried out using a stoichiometric or near stoichiometric amounts of water and a catalyst for hydrolysis and condensation. Stoichiometric amounts of water, or, an amount of water greater than stoichiometric, results in low molecular weight materials, which is one of the objectives of the method in this invention. Caution should be noted for the use of substantially lesser amounts of water as that will result in a residual amount of alkoxy in the material which is undesirable for purposes of this invention.

It is believed by the inventors herein that the key to this invention is the use of the molecule {W(OR″′)₄}_(y) as the third component of this invention. W in the case of this invention is independently selected from the group consisting of Si, Ti, Zr, and A1. Preferred for this invention is Si and Ti and most preferred is Si.

The (OR″′) group is selected from the group consisting of —OCH₃, —OCH₂CH₃, —OCH(CH₃)₂, —O(CH₂)₂CH₃, —OCH₂CH(CH₃)₂, —O(2-ethylhexyl), acetoxy, and, oximo. Preferred for this invention are the groups —OCH₃, —OCH₂CH₃, and —OCH(CH₃) and most preferred are the —OCH₃and —OCH₂CH₃groups. Preferred orthosilicates and orthotitanates for this invention are Si(OCH₂CH₃)₄and Ti(—OCH(CH₃)₂)₄.

Stoichiometry is based on the number of hydrolysable groups on the combined components. The reaction is carried out in the presence of base or acid, with acid being the preferred catalyst. The acid catalysts are preferred to be HC1,phosphoric, and acetic acids, with HC1 and phosphoric acids being most preferred.

Bases that are useable herein are amines, NaOH, KOH and the like and preferred for this invention is NaOH. The hydrolysis reaction is carried out by combining the components in a predetermined ratio and then adding acidic or basic water to the components at a controlled rate to form silanols from the alkoxy moieties. For some end use applications of the inventive materials, a slightly higher molecular weight (higher number of silanol reactive groups) is preferred and in this case, the silicate component is treated for a short period of time by acidic or basic water to cause the silicate component to hydrolyze and condense before the other components are added.

By the preferred means, the following reaction sequence is achieved:

No heat is used in this reaction as higher temperatures (in excess of about 150° C.) may result in a gelation of the reaction mixture. There is a small exotherm from the hydrolysis reaction but the heat is not sufficient to provide problems with the resultant product. No solvents are required in this reaction, but it is within the scope of this invention to utilize solvents. It should be noted that the byproduct of the hydrolysis reaction is alcohol. Typically, the products of this reaction do not need filtration.

As mentioned Supra, it is possible to enhance the molecular weight and thereby increase the amount of silanol functionality on the molecule by first mildly hydrolyzing the ortho precursor and then adding the remainder of the components.

Thus, a molecule having the following average formula may be obtained:

One can also provide a material having the formula:

by hydrolyzing the components (CH₃O)₃Si(CH2)₃OOC(CH₃)C═CH₂,1Si(OCH₂CH₃)₄ and 2 (CH₃O)₃Si(R⁵)₂CdH_(2d)P⁺(R⁶)₃C1⁻.

A preferred material is:

The materials are liquids as prepared. In some cases, if preferred, the by-produced alcohols and any residual water can be removed to provide a solid material, and in some cases the solid material may be hard and appear to be almost crystalline and in some cases, the material may be waxy or paste-like.

These compositions of matter have anti-microbial properties and adhesion properties and are highly dispersible in aqueous solutions. The presence of a large number of silanols on the molecules of this invention creates a solubility or disperseability of these molecules in aqueous solutions that is not obtainable from prior art anti-microbial monomers. The materials of this invention are also suitable for providing adhesion in combination with ionomers, especially glass ionomers.

EXAMPLES

TEOS Tetraethylorthosilicate Z-6070 MTM methyltrimethoxysilane Z-6030 MAPTMS methacryloxypropyltrimethoxysilane 8405 N-(trimethoxysilylpropyl) isothiuronium chloride 2417 2-(4-chlorosulfonylphenyl) ethyltrimethoxysilane The tetraethylorthosilicate or tetrabutyltitanate were placed in a 40 ml vial with a magnetic stirring bar. The functional trialkoxy-silane was added and allowed to mix for 30 minutes. Water, adjusted with KOH to pH 10 or HC1 to pH 2, was added dropwise with agitation. This was allowed to hydrolyze for 60 minutes and 24 hours after which the solution was evaluated for appearance. All weights are in grams. Compound molecular weights were used to calculate the moles and molar ratios of each component.

TABLE 1 Sample # Mw 1 2 3 4 5 6 7 Z-6030 248 2.48 2.48 2.48 Z-6070 136  1.36 1.36 1.36 TEOS 208  2.08 2.08 6.24 2.08 2.08 2.08 6.24 8405 @ 50% in water 274.8 5.5 (2.75) 5.5 (2.75) 5.5 (2.75) 22 (11) 2.75 5.5  2.75 water pH = 10 18 1.8  1.8  1.8  1.8  Moles-6070/TEOS/8405 1/1/2 1/1/2 1/3/1 0/1/4 Moles-6030/TEOS/8405 1/1/1 1/1/2 1/3/1 Solution @ 24 hours soft gel OK clear OK clear OK OK OK OK Application, microbial kill 99.99

TABLE 2 Sample # 8 9 10 11 12 13 14 Z-6030 248 2.48 2.48 2.48 Z-6070 136 1.36 1.36 1.36 TEOS 208 2.08 2.08 6.24 2.08 2.08 2.08 6.24 2417 @ 50% in MeCl 324.85 6.5 (3.25) 6.5 (3.25) 6.5 (3.25) 26 (13) 3.25 6.5  3.25 water pH = 10 18 1 1.8  1.8  1.8  1.8  1.8  1.8  Moles-6070/TEOS/2417 1/1/1 1/1/1 1/3/1 0/1/4 Moles-6030/TEOS/2417 1/1/1 1/1/2 1/3/1 Solution @ 24 hours 2 phase OK OK OK OK OK OK Application, microbial kill miscible 99.99

Purpose

The purpose of this study was to evaluate the effectiveness of test materials labeled #1 and #8, in killing or reducing Escherichia coli (E. coli). The standard pour plate count test method was used to evaluate Percent Reduction of Colony Forming Units (CFU).

Study Design

The E.coli (lot number 168756) was purchased from Quanti-Cult™ and is derived from original ATCC® stock cultures. They are received dehydrated. A viable streak plate was colonized from this culture. One colony was transferred to 5 ml of sterile Tryptic Soy Broth (lot # A3303) and incubated overnight.

Anti-microbial activity is determined by comparing results from the test sample to simultaneously run controls or from the T₀. The concentration of the suspension is determined using serial dilution and plate counts to determine the amount of Colony Forming Units (CFU's)/ml of suspension.

The materials tested in this study are described in the Purpose section of this report. Sterile 0.3 mM KH₂PO₄ buffer was inoculated to a concentration of ^(˜)1.0-3.0×10⁵CFU/ml. A T₀ plate originated from the inoculated buffer for quantification and prepared 1:100 dilution to insure that viable inoculum was applied in the test system. The test materials were formulated in 20×150 ml test tubes. Aliquots of 0.3 grams of each of the materials (#1 and #8) were added to sterile test tubes. Five ml of Tryptic Soy Broth was added to each tube and the tubes inoculated with 1×10⁵ CFU, E. coli. The materials were incubated for 48 hours. To of the inoculums was 9.6×10⁴ CFU/ml. One milliliter aliquots of the test article inoculums were added to Petri dishes, Plate Count Agar added and swirled and the plates were incubated at 35° C. overnight.

Results

The results show 16 CFU/ml for material #1 or >99.9% reduction and material #8 had 0 CFU/ml (no growth) or 100% reduction. 

What is claimed is:
 1. A method of reducing the number of one or more micro-organisms, said method comprising: i. providing one or more micro-organisms; ii. treating said one or more micro-organisms provided with a composition having the average formula:

 wherein the average molar ratio of x:y:z is 0.25-3:4:0.25-3, with the proviso that there is present at least one RSi-unit and at least one R′Si unit;  wherein W is independently selected from the group consisting essentially of Si, Ti, and Zr, and Al;  wherein R is a cure functionality based on the chemistry selected from the group consisting of glycidoxy, amino, acrylamide, methacrylamide, acrylate, methacrylate, C₂-C₈alkenyl, mercapto, ester, isocyanato, epoxycyclohexyl, carboxylic acid, and

  wherein p has a value of from 1 to 6;   wherein R³ is selected from the group consisting of hydroxyl and alkoxy  groups having 1 to 4 carbon atoms;  wherein R² is independently selected from the group consisting of hydroxyl groups,

wherein s has a value of about 1 to 5; wherein y has a value of 4; wherein R¹ is selected from the group consisting of: a. a sulfonium salt of the formula: Si(R⁵)₂C_(d)H_(2d)S⁺(R⁴)₂X⁻   wherein R⁴ is independently an alkyl group or aralkyl group  wherein there is a total of less than 60 carbon atoms in the molecule, R⁵ is independently selected from the group consisting of hydroxyl groups,

 wherein d is an integer of 1 or greater, and  wherein X⁻ is a water soluble monovalent anion; b. an isothiuronium salt of the formula: Si(R⁵)₂C_(d)H_(2d)S⁺C(NH₂)₂X⁻,  wherein R⁵ is independently selected from the group consisting of hydroxyl groups,

 wherein d is an integer of 1 or greater, and  wherein X⁻ is a water soluble monovalent anion; c. a phosphonium salt of the formula: Si(R⁵)₂C_(d)H_(2d)P⁺(R⁶)₃X⁻  wherein R⁶ is independently selected from an alkyl group or aralkyl group wherein there is a total of less than 60 carbon atoms in the molecule, R⁵ is independently selected from the group consisting of hydroxyl groups,

 wherein d is an integer of 1 or greater, and  wherein X⁻ is a water soluble monovalent anion; and d. an amine of the formula: Si(R⁵)₂C_(d)H_(2d)N(H)(C_(d)H_(2d))NH₂  wherein R⁵ is independently selected from the group consisting of hydroxyl groups,

 wherein d is an integer of 1 or greater; and wherein (WO_(y)) is derived from W(OR⁷)₄where (OR⁷) is independently selected from the group consisting of: A.—OCH₃, B.—OCH₂CH₃, C.—OCH(CH₃)₂, D.—O(CH₂)₃CH₃, E.—OCH₂CH(CH₃)₂, F.—O(2-ethylhexyl), G. acetoxy, and H. oximo.
 2. The method of claim 1, wherein said composition has anti-microbial and/or adhesion properties.
 3. The method of claim 1, wherein said one or more micro-organisms are one or more bacteria.
 4. The method of claim 1, wherein said one or more bacteria are Escherichia coli (E. coli).
 5. The method of claim 1, wherein said one or more micro-organisms are one or more viruses.
 6. The method of claim 1, wherein said one or more micro-organisms are one or more algae.
 7. The method of claim 1, wherein said one or more micro-organisms are one or more mildews.
 8. The method of claim 1, wherein said one or more micro-organisms are one or more molds.
 9. The method of claim 1, further comprising the step of providing said composition with one or more ionomers.
 10. The method of claim 9, wherein said one or more ionomers are one or more glass ionomers.
 11. The method of claim 9, wherein said one or more ionomers are one or more modified glass ionomers.
 12. The method of claim 9, further comprising the step of applying said composition to a surface or substrate.
 13. The method of claim 1, further comprising adding said composition into an aqueous solution.
 14. The method of claim 13, wherein said composition is soluble and dispersible within said aqueous solution.
 15. The method of claim 14, wherein said solubility and disperseability of said composition within said aqueous solution is due to a large number of silanols.
 16. The method of claim 1, wherein said method providing said composition is performed without the addition of heat to reduce gelation of said composition.
 17. The method of claim 1, wherein said composition is a gel or a liquid.
 18. The method of claim 1, further comprising the step of removing an amount of water from said composition to provide a substantially solid material.
 19. The method of claim 18, wherein said solid material composition is substantially crystalline, substantially waxy, or substantially paste-like.
 20. The method of claim 1, further comprising the step of providing a catalyst for hydrolysis and condensation of said composition. 